EP1745086B1 - Polymeres electroluminescents - Google Patents

Polymeres electroluminescents Download PDF

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Publication number
EP1745086B1
EP1745086B1 EP05742884A EP05742884A EP1745086B1 EP 1745086 B1 EP1745086 B1 EP 1745086B1 EP 05742884 A EP05742884 A EP 05742884A EP 05742884 A EP05742884 A EP 05742884A EP 1745086 B1 EP1745086 B1 EP 1745086B1
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occurrence
identically
differently
group
atoms
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EP1745086A1 (fr
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Arne BÜSING
René SCHEURICH
Susanne Heun
Ingrid MICHAELSEN
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Merck Patent GmbH
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Merck Patent GmbH
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • PLEDs polymer OLEDs
  • Both methods have the advantage that the compounds can be processed from solution and that no expensive and expensive vapor deposition process is required, as is the case for devices based on low molecular weight compounds.
  • NS Baek et al. (Thin Solid Films 2002, 417, 111 ) describe ruthenium-containing organosilane polymers as red-emitting materials.
  • the intensity of the red bands at room temperature is weak due to nonradiative relaxation. Only at low temperatures, which are prohibitive for the usual use of OLEDs, higher intensities were measured. These materials are therefore obviously not suitable for use in PLEDs, since there is a high Lumineszenzquantenausbeute necessary for good efficiency even at room temperature. This suggests that the combination of ruthenium complexes with organosilanes may not be suitable for efficient emission.
  • platinum (II) -saturated silylacetylene polymers W.-Y.
  • Light-emitting polymers which have metal complexes in the side chain are of S.Tokito et al. (Organic Electronics, Vol. 4 (2003) 105-111 ) disclosed.
  • Conjugated polymers which, in addition to spirobifluorene units or besides spirobifluorene and fluorene units, also contain metal complexes as structural units, are described in US Pat WO 03/020790 A2 and the WO 02/077060 A1 disclosed.
  • Block copolymers containing polysilane and organic polymer blocks are disclosed in U.S.Pat EP 0266693 A2 disclosed. Electrically conductive polysilanes are used in the DE 3634281 A1 disclosed. The preparation of specific polymers containing both silyl units and thiophenediyl units is described in U.S. Pat FR 2655655 A1 described.
  • copolymers hitherto unknown, which contain certain organosilane units and emitting iridium complexes covalently bonded, have marked improvements compared with polymers and mixtures according to the prior art, in particular high emission efficiency and low operating voltages.
  • organosilane polymers with other emitting metals ruthenium, platinum
  • the same polymer matrix shows good results for both green and red triplet emitters. It is a distinct technological advantage to be able to use a matrix for multiple or, ideally, all emission colors without having to optimize a separate matrix for each emitter.
  • An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which does not necessarily contain only aromatic or heteroaromatic groups, but in which also several aromatic or heteroaromatic groups are replaced by a short non-aromatic unit (less than 10%).
  • the atoms other than H, preferably less than 5% of the atoms other than H), such as sp 3 -hybridized C, O, N, etc. may be interrupted.
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also to be understood as aromatic ring systems for the purposes of this invention.
  • An aromatic ring system contains at least 6 C atoms, while a heteroaromatic ring system contains at least 2 C atoms and at least one heteroatom, preferably selected from N, O and / or S, and the sum of C atoms and heteroatoms is at least 5.
  • a C 1 - to C 40 -alkyl group in which also individual H atoms or CH 2 groups can be substituted by the abovementioned groups particularly preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, Cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexen
  • a C 1 - to C 40 -alkoxy group is particularly preferably understood as meaning methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy or 2-methylbutoxy.
  • aryl or heteroaryl group which may be monovalent or bivalent depending on the use, which may be substituted in each case with the abovementioned radicals R 1 and which may be linked via any position on the aromatic or heteroaromatic, are especially groups understood which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzpyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, Isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7
  • Aromatic ring systems are understood more particularly to mean biphenyls, terphenyls, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene or cis- or trans-indenofluorene.
  • the structural unit according to formula (1) may be bonded either in the side chain or in the main chain of the polymer. If X stands for a monovalent group R 3 , then the structural unit according to formula (1) is bound in the side chain of the polymer. If X is a bivalent group - (Y) p-, then the structural unit according to formula (1) is bound in the main chain of the polymer.
  • the copolymer of the invention may be conjugated, partially conjugated or nonconjugated. It is preferably conjugated or partially conjugated.
  • Conjugated polymers in the context of this invention are polymers which contain in the main chain mainly sp 2 -hybridized (or sp-hybridized) carbon atoms, which may also be replaced by corresponding heteroatoms. In the simplest case this means alternating presence of double and single bonds in the main chain. Mainly, of course, that of course (without further action) occurring defects that lead to conjugation interruptions, do not devalue the term "conjugated polymer".
  • conjugated if in the main chain Arylaminein fraud, Arylphosphinechen and / or certain heterocycles (ie conjugation of N, O, S or P atoms) and / or organometallic complexes such as iridium Complexes (conjugation via the metal atom).
  • conjugated is the so-called ⁇ -conjugation, that is, for example, the conjugation via a silicon atom.
  • Partially conjugated polymers for the purposes of this invention are polymers which either contain longer conjugated portions in the main chain which are interrupted by non-conjugated portions or which have longer conjugated portions in the side chains of a polymer which is not conjugated in the main chain contain. By contrast, units such as simple alkylene chains, (thio) ether bridges, ester, amide or imide linkages are clearly defined as non-conjugated segments.
  • the copolymers according to the invention may contain, in addition to the units according to formula (1) and apart from the iridium complex, various further structural elements. These may be, inter alia, structural units which may form the polymer backbone, or structural units which influence the charge injection or charge transport properties. Such units are for example in WO 03/020790 and WO 05/014689 described in detail.
  • the copolymers according to the invention may have random, alternating or else block-like structures or alternatively have several of these structures in turn.
  • the polymers may be linear, branched or dendritic. By using several different structural elements properties such. Solubility, solid phase morphology, etc., can be adjusted.
  • the polymers are linear.
  • the molecular weight M w of the polymers is between 10 3 and 10 7 g / mol, preferably between 10 4 and 10 6 g / mol, more preferably between 5 ⁇ 10 4 and 8 ⁇ 10 5 g / mol.
  • the polymers according to the invention are prepared by polymerization of corresponding monomers, where at least one monomer in the polymer leads to units of the formula (1) and at least one monomer contains the iridium complex or a ligand for the coordination of iridium.
  • at least one monomer in the polymer leads to units of the formula (1) and at least one monomer contains the iridium complex or a ligand for the coordination of iridium.
  • some types have proven that all lead to C-C bonds (SUZUKI coupling, YAMAMOTO coupling, STILLE coupling). How the polymerization can be carried out by these methods and how the polymers can then be separated and purified from the reaction medium is described in detail, for example WO 04/037887 described.
  • the appropriately substituted iridium complex is used directly as a monomer. However, it may also be preferred to use an appropriately substituted ligand in the polymerization reaction and to carry out the complexation of the iridium on the finished polymer.
  • A is the same or different Si or Ge, particularly preferably Si, for each occurrence.
  • Y is particularly preferably identical or different at each occurrence, identically or differently, an aromatic ring system having 2 to 16 C atoms or spirobifluorene, which may be substituted in each case by one or more radicals R 4 .
  • R 1 , R 2 , R 3 are as defined above, wherein at each structural unit according to formula (1) at least one of the substituents R 1 to R 3 is an aromatic or heteroaromatic ring system having 2 to 25 C-atoms represents, which may be substituted with one or more substituents R 4 ; each preferably identically or differently, each of the radicals R 1 , R 2 and R 3 is an aromatic or heteroaromatic ring system having 2 to 16 C atoms or spirobifluorene, each of which may be substituted by one or more substituents R 4 .
  • the index n is identical or different at each occurrence 1, 2 or 3, particularly preferably 1 or 2.
  • the index p is identical or different at each occurrence 1 or 3, particularly preferably 1.
  • Examples of preferred units according to formula (1) are substituted or unsubstituted structures according to the depicted examples (1) to (27), wherein the dashed bonds signify a linkage in the polymer;
  • Examples (1) to (15) are examples of structural units according to formula (1) which are bonded to the main chain;
  • Examples (16) to (27) are examples of structural units according to formula (1) which are linked in the side chain.
  • Alkyl represents a straight, branched or cyclic alkyl chain which may be substituted or unsubstituted as defined for R 1 , R 2 , R 3 . Potential substituents are usually not shown because of the better clarity.
  • Example 1 Example 2
  • Example 4 Example 5
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Example 11
  • Example 12 Example 13
  • Example 14 Example 15
  • Example 16 Example 17
  • Example 18 Example 19
  • Example 20 Example 21
  • Example 22 Example 23
  • Example 24 Example 25
  • Example 26 Example 27
  • the iridium complexes bound in the copolymer are preferably organometallic complexes which can emit light from the triplet state at room temperature. Without wishing to be bound by any particular theory, for purposes of this application all emitting iridium complexes are referred to as triplet emitters.
  • An organometallic compound is to be understood as meaning a compound which has at least one direct metal-carbon bond. Further preferred are neutral iridium complexes, in particular neutral iridium (III) complexes.
  • Preferred ligands L are monoanionic ligands, such as 1,3-diketonates derived from 1,3-diketones, such as.
  • 1,3-diketonates derived from 1,3-diketones
  • ethyl acetoacetate carboxylates derived from aminocarboxylic acids, such as.
  • pyridine-2-carboxylic acid quinoline-2-carboxylic acid, glycine, dimethylglycine, alanine, dimethylaminoalanine, or salicyliminates derived from salicylimines, such as.
  • salicylimines such as.
  • methylsalicylimine ethylsalicylimine, phenylsalicylimine.
  • polynuclear iridium complexes and iridium clusters are also preferred.
  • the iridium complex is covalently incorporated into the polymer chain.
  • functional polymerizable groups must be present on the complex. Examples of corresponding brominated complexes used as monomers in polycondensation reactions (e.g. according to SUZUKI or according to YAMAMOTO) are used in WO 02/068435 and in the undisclosed application DE 10350606.3 described.
  • polystyrene resin it may also be preferred to add further conjugated, partially conjugated or non-conjugated polymers, oligomers, dendrimers or other low molecular weight compounds to the polymer.
  • further components may prove useful for some applications: For example, by adding an electronically active substance, the hole or electron injection or the hole or electron transport in the corresponding blend can be regulated.
  • the additional component can also improve singlet-triplet transfer or self-emit light.
  • the addition of electronically inert compounds may also be helpful to control, for example, the viscosity of a solution or the morphology of the film formed.
  • the blends thus obtained are also the subject of the invention.
  • the invention further provides solutions and formulations of one or more copolymers of the invention or blends in one or more solvents.
  • polymer solutions can be made is for example in WO 02/072714 , in WO 03/019694 and described in the literature cited therein.
  • These solutions can be used to prepare thin polymer layers, for example by area coating techniques (eg, spin coating) or printing processes (eg, inkjet printing).
  • electroluminescent materials emitting materials
  • a general method is usually used, which must be adapted accordingly for the individual case. Such a method has been used, for example, in WO 04/037887 described in detail.
  • the invention therefore also relates to the use of a copolymer according to the invention in a PLED as electroluminescent material.
  • the invention likewise provides a PLED having one or more layers, wherein at least one of these layers contains at least one copolymer according to the invention.
  • the polymer was precipitated by dropping in twice the amount of methanol and dissolved in toluene. After filtration through Celite was precipitated again with methanol and the polymer dried in vacuo.
  • polymers P2 , P3 and P4 Further polymers according to the invention (polymers P2 , P3 and P4 ) were prepared according to the synthesis of polymer P1 .

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Claims (25)

  1. Copolymères contenant
    (A) 1-99,99 mol% d'au moins une unité structurelle de la formule (1),
    Figure imgb0091
     dans laquelle ce qui suit s'applique aux symboles et indices utilisés :
    A est, pour chaque occurrence, de manière identique ou différente, Si, Ge, Sn ou Pb ;
    Y est, pour chaque occurrence, de manière identique ou différente, un système de cycle aromatique ou hétéroaromatique divalent comportant de 1 à 40 atomes de C, lesquels peuvent être substitués par un ou plusieurs radicaux R4, un groupe vinylène -CR4=CR4- ou un groupe acétylène -C≡C- ;
    X est, pour chaque occurrence, de manière identique ou différente, un groupe divalent -(Y)p- ou un groupe monovalent R3 ;
    R1, R2, R3 sont, pour chaque occurrence, de manière identique ou différente, H, F, CN, N(R4)2, un groupe alkyle, alcoxy ou thioalcoxy en chaîne droite, ramifié ou cyclique comportant de 1 à 40 atomes de C, lesquels peuvent être substitués par R4 ou également non substitué, où un ou plusieurs groupes CH2 non adjacents peut/peuvent être remplacé(s) par -R5C=CR5-, -C≡C-, Si(R5)2, Ge(R5)2, Sn(R5)2, C=O, C=S, C=Se, C=NR5, -O-, -S-, -NR5- ou -CONR5- et où un ou plusieurs atomes de H peut/peuvent être remplacé(s) par F, Cl, Br, I, CN, OH ou NO2, ou un système de cycle aromatique ou hétéroaromatique ou un groupe aryloxy ou hétéroaryloxy, chacun comportant de 2 à 40 atomes de C aromatiques, dont chacun peut être substitué par un ou plusieurs radicaux R4, ou une combinaison de ces systèmes ; deux substituents R1, R2 et/ou R3 ou plus peuvent ici former un autre système de cycle aliphatique ou aromatique monocyclique ou polycyclique, l'un avec l'autre;
    R4 est, pour chaque occurrence, de manière identique ou différente, H, F, Cl, Br, I, CN, NO2, une chaîne alkyle ou alcoxy en chaîne droite, ramifiée ou cyclique comportant de 1 à 22 atomes de C, où, en outre, un ou plusieurs atomes de C non adjacents peut/peuvent être remplacé(s) par -R5C=CR5-, -C≡C-, Si(R5)2, Ge(R5)2, Sn(R5)2, -NR5-, -O-, -S-, -CO-O- ou -O-CO-O- et où un ou plusieurs atomes de H peut/peuvent être remplacé(s) par F, Cl, Br, I, CN ou NO2, un groupe aryle, hétéroaryle ou aryloxy comportant de 1 à 40 atomes de C, lesquels, en outre, peuvent être substitués par un ou plusieurs radicaux R5, ou OH, N(R5)2, B(R5)2 ou Si(R5)3 ;
    R5 est, pour chaque occurrence, de manière identique ou différente, H ou un radical hydrocarbone aliphatique ou aromatique comportant de 1 à 20 atomes de C ;
    n est, pour chaque occurrence, de manière identique ou différente, 1, 2, 3 ou 4;
    p est, pour chaque occurrence, de manière identique ou différente, 1, 2 ou 3 ;
    la liaison en pointillés représente le lien sur le polymère ;
    et
    (B) 0,01 - 50 mol% d'au moins un complexe d'iridium lié de façon covalente, lequel émet de la lumière depuis l'état triplet.
  2. Copolymères selon la revendication 1, caractérisés en ce que X représente un groupe R3, et l'unité structurelle de la formule (1) est liée dans la chaîne latérale du polymère.
  3. Copolymères selon la revendication 1, caractérisés en ce que X représente un groupe divalent -(Y)p-, et l'unité structurelle de la formule (1) est liée dans la chaîne principale du polymère via les deux groupes Y.
  4. Copolymère selon les revendications 1 à 3, caractérisé en ce que le complexe d'iridium est incorporé dans la chaîne latérale du polymère.
  5. Copolymère selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le complexe d'iridium est incorporé dans la chaîne principale du polymère.
  6. Copolymère selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'il est conjugué ou partiellement conjugué.
  7. Copolymère selon une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'il contient d'autres éléments structurels en plus des unités de la formule (1) et en plus du complexe d'iridium.
  8. Copolymère selon la revendication 7, caractérisé en ce que les autres unités structurelles forment l'ossature de polymère et/ou améliorent les propriétés d'injection de charges ou de transport de charges.
  9. Copolymères selon une ou plusieurs des revendications 1 à 8, caractérisés en ce que le symbole A, de manière identique ou différente pour chaque occurrence, représente Si ou Ge.
  10. Copolymères selon une ou plusieurs revendications 1 à 9, caractérisés en ce que le symbole Y, de manière identique ou différente pour chaque occurrence, représente un système de cycle aromatique comportant de 2 à 25 atomes de C, lesquels peuvent être substitués par un ou plusieurs radicaux R4, un groupe vinylène -CR4=CR4- ou un groupe acétylène -C≡C-, étant entendu qu'un groupe vinylène ou un groupe acétylène peut seulement être lié à un système aromatique.
  11. Copolymères selon une ou plusieurs des revendications 1 à 10, caractérisés en ce que les symboles R1, R2, R3, de manière identique ou différente pour chaque occurrence, sont comme défini sous la revendication 1, où au moins l'un des substituents R1 à R3 représente un système de cycle aromatique ou hétéroaromatique comportant de 2 à 25 atomes de C, lesquels peuvent être substitués par un ou plusieurs substituents R4.
  12. Copolymères selon une ou plusieurs des revendications 1 à 11, caractérisés en ce que l'indice n, de manière identique ou différente pour chaque occurrence, est 1, 2 ou 3.
  13. Copolymères selon une ou plusieurs des revendications 1 à 12, caractérisés en ce que l'indice p, de manière identique ou différente pour chaque occurrence, est 1 ou 3.
  14. Copolymères selon une ou plusieurs des revendications 1 à 13, caractérisés en ce que les unités structurelles de la formule (1) présentent une structure symétrique.
  15. Copolymères selon une ou plusieurs des revendications 1 à 14, caractérisés en ce que les unités structurelles de la formule (1) sont choisies parmi les exemples (1) à (27),
    Figure imgb0092
    Figure imgb0093
    Figure imgb0094
         Exemple 1 Exemple 2 Exemple 3
    Figure imgb0095
    Figure imgb0096
    Figure imgb0097
         Exemple 4 Exemple 5 Exemple 6
    Figure imgb0098
    Figure imgb0099
    Figure imgb0100
         Exemple 7 Exemple 8 Exemple 9
    Figure imgb0101
    Figure imgb0102
    Figure imgb0103
         Exemple 10 Exemple 11 Exemple 12
    Figure imgb0104
    Figure imgb0105
    Figure imgb0106
         Exemple 13 Exemple 14 Exemple 15
    Figure imgb0107
    Figure imgb0108
    Figure imgb0109
         Exemple 16 Exemple 17 Exemple 18
    Figure imgb0110
    Figure imgb0111
    Figure imgb0112
         Exemple 19 Exemple 20 Exemple 21
    Figure imgb0113
    Figure imgb0114
    Figure imgb0115
         Exemple 22 Exemple 23 Exemple 24
    Figure imgb0116
    Figure imgb0117
    Figure imgb0118
         Exemple 25 Exemple 26 Exemple 27
    lesquelles unités peuvent être substituées ou non substituées.
  16. Copolymères selon une ou plusieurs des revendications 1 à 15, caractérisés en ce qu'ils contiennent 5-80 mol% d'unités structurelles de la formule (1).
  17. Copolymères selon une ou plusieurs des revendications 1 à 16, caractérisés en ce que ce sont des complexes d'iridium organométalliques.
  18. Copolymères selon une ou plusieurs des revendications 1 à 17, caractérisés en ce que les complexes d'iridium contiennent trois ligands chélatants bidentés.
  19. Copolymères selon les revendications 17 et 18, caractérisés en ce que les complexes d'iridium présentent une structure conformément à la formule (2):
    Figure imgb0119
     dans laquelle R5 est comme défini sous la revendication 1, et ce qui suit s'applique aux autres symboles utilisés :
    DCy est, pour chaque occurrence, de manière identique ou différente, un groupe cyclique qui contient au moins un atome de donneur, de préférence azote ou phosphore, via lequel le groupe cyclique est lié à l'iridium et qui peut à son tour supporter un ou plusieurs substituents R6 ; les groupes DCy et CCy sont liés l'un à l'autre via une liaison covalente ;
    CCy est, pour chaque occurrence, de manière identique ou différente, un groupe cyclique qui contient au moins un atome de carbone via lequel le groupe cyclique est lié à l'iridium et qui peut à son tour supporter un ou plusieurs substituents R6 ;
    L est, pour chaque occurrence, de manière identique ou différente, un ligand chélatant bidenté ;
    R6 est, pour chaque occurrence, de manière identique ou différente, H, F, Cl, Br, I, NO2, CN, un groupe alkyle ou alcoxy cyclique en chaîne droite ou ramifié comportant de 1 à 40 atomes de C, où un ou plusieurs groupes CH2 non adjacents peut/peuvent être remplacé(s) par C=O, C=S, C=Se, C=NR5, -R5C=CR5-, -C≡C-, -O-, -S-, -NR5-, Si(R5)2 ou -CONR5- et où un ou plusieurs atomes de H peut/peuvent être remplacé(s) par F, Cl, Br, I, CN ou NO2, ou un système de cycle aromatique ou hétéroaromatique comportant de 2 à 40 atomes de C, lesquels peuvent être substitués par un ou plusieurs radicaux R6 non aromatiques ; où une pluralité de substituents R6, à la fois sur le même cycle et également sur les deux cycles différents, peuvent ensemble à leur tour former un autre système de cycle monocyclique ou polycyclique, aliphatique ou aromatique ;
    m est, pour chaque occurrence 1, 2 ou 3 ;
    le lien sur le polymère est réalisé ici soit via un ligand, soit via une pluralité de ligands.
  20. Copolymères selon la revendication 19, caractérisé en ce que le ligand L est un ligand monoanionique choisi parmi le groupe des 1,3-dicétonates dérivés des 1,3-dicétones, des 3-cétonates dérivés des 3-cétoesters, des carboxylates dérivés des acides aminocarboxyliques ou des salicyliminates dérivés des salicylimines.
  21. Copolymères selon une ou plusieurs des revendications 1 à 20, caractérisés en ce que la proportion des complexes d'iridium complexes dans le polymère est de 1 - 25 mol%.
  22. Mélanges (blends) d'au moins un copolymère selon une ou plusieurs des revendications 1 à 21 avec un ou plusieurs polymères, oligomères ou composés de poids moléculaire faible conjugués, partiellement conjugués ou non conjugués.
  23. Utilisation d'un copolymère selon une ou plusieurs des revendications 1 à 22 dans un dispositif électronique organique.
  24. Dispositif électronique organique comportant une ou plusieurs couches, où au moins l'une de ces couches comprend au moins un copolymère ou un mélange selon une ou plusieurs des revendications 1 à 22.
  25. Dispositif électronique organique selon la revendication 24, caractérisé en ce qu'il concerne des diodes émettrices de lumière organiques (PLED), des cellules solaires organiques (O-SC), des dispositifs optiques non linéaires, un doublage de fréquence (conversion élévatrice), des détecteurs optiques organiques, des dispositifs d'extinction de champ organiques (O-FQD) ou des diodes laser organiques (O-laser).
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